JPS6263530A - Catalyst for converting c3 and c4 hydrocarbon and conversiontherefor - Google Patents

Abstract

Novel compositions of matter include: mixed oxides of (a) at least one oxide of chromium, at least one oxide of manganese and at least one oxide of magnesium, Lanthanum Series metals, preferably lanthanum and cerium, and/or niobium; (b) at least one oxide of chromium, at least one oxide of calcium, strontium, tin and/or antimony, at least one oxide of manganese and at least one oxide of magnesium, Lanthanum Series metals and/or niobium; - (c) at least one oxide of chromium, at least one oxide of iron and at least one oxide of magnesium, , Lanthanum Series metals and/or niobium; and (d) at least one oxide of chromium, at least one oxide of liron, at least one oxide of manganese and at least one oxide of magnesium, Lanthanum Series metals and/or niobium. These compositions are particularly effective as catalyst compositions for the conversion of C, and C, hydrocarbons to less saturated hydrocarbons, with high selectivities to ethylene and ethane and particularly ethylene, and the addition of the chromium significantly extends the activity of the catalyst for such selective conversion before regeneration is necessary. A method of converting C, and C, hydrocarbons to less saturated hydrocarbons, and selectively to ethylene and ethane and particularly ethylene, is also disclosed. Carrying out the process in the presence of steam is essential to the process when the catalyst contains iron and is optional when the catalyst does not contain iron. Limiting the amount of bound or fixed sulfur in the catalyst also improves the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved compositions of matter. More particularly, the present invention relates to improved catalysts for converting C1 and C4 hydrocarbons to less saturated hydrocarbons. More particularly, the present invention relates to improved catalysts for converting C3 and C4 alkanes to less saturated hydrocarbons, particularly ethylene and propylene, and preferably ethylene.

Olefins such as ethylene and propylene are major raw materials for the organic chemistry and petrochemical industries. Among the olefins, ethylene is the most important chemical raw material because the demand for ethylene is about twice that of propylene. Therefore, low value hydrocarbons can be converted into ethylene and propylene,
In particular, improved methods for conversion to ethylene are highly desirable.

Many proposals have been made for producing ethylene and propylene, particularly ethylene, from a variety of feedstocks by a wide variety of methods.

Currently, ethylene is mostly produced by dehydrogenation or pyrolysis of ethane and propane, naphtha, and in certain cases gas oils. Natural gas contains about 5 to 60% by volume of hydrocarbons (C2 or higher) other than methane, so about 75% of the ethylene currently produced in the United States is made from natural gas ethane and higher carbonized gases. Manufactured by steam decomposition of hydrogen components. However, in most cases, the amount of ethane and higher normally gaseous hydrocarbons in natural gas is less than about 25%, and usually less than about 15%.

Therefore, ethylene and propylene (especially ethylene)
These limited amounts of raw materials available for the production of must be used efficiently. Unfortunately, these conventional methods result in low conversion to olefins and
Moreover, the conventional process is highly energy-intensive as it has poor selectivity to ethylene rather than propylene and requires relatively harsh conditions, especially temperatures above about 1000°C.

In order to reduce the severity of the conditions and, more importantly, to improve the conversion of normally gaseous feedstocks to ethylene and propylene and the selectivity to ethylene, there are many methods, including the use of solid contact materials. has been proposed. Some of these proposals utilize inert solid contact materials,
It also improves contact between the feed hydrocarbon and steam and maintains a more uniform temperature throughout the reaction zone. In other cases, the solid contact material is a catalyst. The above-mentioned use of solid contact materials, especially as catalysts, leads to a moderate improvement in the conversion to ethylene and propylene, but only a very small improvement in the selectivity to ethylene. Therefore, the development of improved contacting methods, particularly those that increase selectivity to ethylene rather than propylene, is highly desirable. However, the mode of functioning of such catalysts, why certain components are effective while similar components are not,
There is little understanding of why some combinations of ingredients are effective while others are not; clearly, many theories have been proposed by researchers and others; will only cause confusion. This is because each theory explains why a particular catalytic material works well, but it does not explain why similar catalytic materials do not work and why other dissimilar materials are effective. This is because it is clear. Furthermore, the technology for catalytic conversion of hydrocarbons to olefins remains highly unpredictable.

It is therefore an object of the present invention to provide an improved composition of matter and a method of utilizing said composition, overcoming the aforementioned problems and other disadvantages of the prior art.Another object of the invention The objective is to provide an improved composition of matter. Yet another object of the present invention is to provide improved catalyst compositions for converting C3 and C4 hydrocarbons to less saturated hydrocarbons. Another object of the present invention is to provide an improved method for converting C1 and C1 hydrocarbons to less saturated hydrocarbons in the presence of steam. Yet another object of the present invention is an improvement for converting C1 and C1 hydrocarbons into less saturated hydrocarbons in the presence of steam to selectively produce ethylene, ethane and propylene and especially ethylene. The purpose is to provide a method. A further object of the invention is to
An improved catalyst for the conversion of C3 and C4 hydrocarbons to less saturated hydrocarbons, especially for producing ethylene, ethane and propylene, especially ethylene.
It is an object of the present invention to provide an improved catalyst having an improved useful life before regeneration is required.

The present invention comprises (a) at least one oxide of chromium, at least one oxide of manganese and at least one oxide of magnesium, lanthanum metals (especially lanthanum and cerium), and/or niobium; b) at least one oxide of chromium, calcium, strontium, barium, tin and/or antimony (especially calcium),
At least one oxide of manganese, at least one oxide of magnesium, lanthanum metal and/or niobium: (e> at least one oxide of chromium, at least one oxide of iron, and at least one oxide of magnesium) an oxide, a lanthanum metal and/or niobium; and (d
) at least one oxide of chromium, at least one oxide of iron
An improved material composition is provided that includes oxides of species, at least one oxide of manganese and at least one oxide of magnesium, lanthanum-based metals, and/or niobium. These compositions have been found to be highly effective catalyst compositions for converting feed hydrocarbons consisting of at least one of C1 and C1 hydrocarbons to less saturated hydrocarbons. . The feed hydrocarbons consisting of C3 and C, hydrocarbons are replaced with less saturated hydrocarbons,
in particular to ethylene and propylene, and preferably to ethylene, under conditions suitable to convert the feed hydrocarbons to less saturated product hydrocarbons.
contacting the feed hydrocarbon with the catalyst composition described above. When the catalyst composition contains iron, it is essential to carry out the process in the presence of steam in order to maintain contactability while carrying out the production of olefins, especially ethylene, and the catalyst In the absence of iron, the presence of steam is optional in carrying out the method. The effectiveness of the catalyst composition is also improved by limiting the sulfur content in the catalyst.

The hydrocarbon feed component according to the invention contains sufficient amounts of C0 and C.
There is a standard gaseous hydrocarbon stream containing four hydrocarbons, especially propane and n-butane, preferably n-butane. The presence of other standard gaseous components or normally liquid components that evaporate under the operating conditions is not detrimental to the process. For example, when utilizing isobutane in accordance with the invention, the catalyst of the invention shifts the product stream from isobutene to propylene;
It has therefore been found that one of the desired products of the invention is produced. On the other hand, the catalytic method of the present invention has been found to be less effective in improving the conversion of ethane to ethylene compared to strictly thermal methods. However, the presence of ethane in the feed hydrocarbon is clearly non-hazardous, the non-hydrocarbon components are also non-hazardous, and the first requirement in all cases is to The cost or difficulty of separating active substances or products of components other than C3 and C1 hydrocarbons and how low cost such separation is before or after carrying out the process of the invention and /or whether it is less difficult. Suitable feedstocks for the process of the invention are obtained from sources such as natural gas, refinery off-gas, and the like. However, the most suitable and plentiful source is the C1 and C1 hydrocarbon streams recovered during the processing of natural gas to produce pipeline gas (city gas) for heating purposes.

Conventionally, C2 and higher hydrocarbons are converted into methane (
C+) to obtain pipeline gas mainly composed of methane for heating. Normally, natural gas is first converted into liquid hydrocarbons (CS+hydrocarbons or natural gasoline) by cooling it to successively lower temperatures, either at the high pressure it produces or compressed to high pressure. ), then successively the 05 hydrocarbons, the C4 hydrocarbons, the C1 hydrocarbons and finally the C2 hydrocarbons, with the condensed liquid remaining unused between each cooling stage. Separated or fractionated from condensed steam. In this way, it is possible to obtain individual streams based on individual hydrocarbons such as Cs, C4, Cz and C2, or to recover streams based on a combination of individual hydrocarbons. I can do it.

However, either the propane or butane stream thus separated can be utilized as the feed hydrocarbon for the present invention, or a stream based on a mixture of propane and butane can be utilized. Clearly, the latter stream would eliminate the need for a single stage of cooling and separation in the natural gas processing system.

The composition of matter of the invention comprises one of the following groups of mixed oxides: (Otori) At least one oxide of chromium, at least one oxide of manganese, at least one oxide of magnesium When using oxides of lanthanum and/or niobium, lanthanum metals are preferably selected from the group consisting of lanthanum and cerium.

(b) at least one oxide of the elements calcium, strontium, barium, tin and/or antimony, at least one oxide of manganese and at least one of magnesium;
oxides of species, lanthanum metals and/or niobium. In the above composition, at least one Group IIA metal selected from the group consisting of calcium, strontium and barium is preferred, with calcium being particularly preferred. The lanthanum-based metal is preferably selected from the group consisting of lanthanum and cerium.

(c) At least one oxide of chromium, at least one oxide of iron and at least one oxide of magnesium, lanthanum metal and/or niobium. Also in this composition, the lanthanum-based metal is preferably selected from the group consisting of lanthanum and cerium.

(d) at least one oxide of chromium, at least one oxide of iron, at least one oxide of manganese, and at least one oxide of magnesium, lanthanum-based metals and/or niobium. The lanthanum-based metal is preferably selected from the group consisting of lanthanum and cerium.

The exact characteristics of these compositions are unknown except that it is believed that all components are present in the oxide state. Therefore, metals may exist as electrically balanced simple oxides or mixtures of oxides and perhaps as electrically balanced mixtures of oxides and partial oxides. For this reason, the values of components present in small amounts in the composition are expressed in terms of weight percent of the metal element, based on the total weight of the composition. Also, sometimes in the specification, each oxide of magnesium, lanthanum metal, and niobium is referred to as the base or base material, and the remaining components are referred to as the active ingredient or promoter. Oxides of magnesium, lanthanum metals and niobium are usually
It is referred to as such for convenience only, as it is present in major amounts and the remaining components are present in minor amounts. Therefore, it should be understood that such designations are not meant to classify the components. As will become clear hereinafter, all components listed are necessary for the process of the invention and are all catalytically active.

As previously mentioned, the above composition of matter has been found to be particularly useful as a catalyst composition for converting C3 and C1 hydrocarbons to less saturated hydrocarbons.

Therefore, the compositions for the above-mentioned uses usually contain a major amount of oxides of magnesium, lanthanum metals and/or niobium and minor amounts of the remaining ingredients. The remaining components are preferably present in an amount of about 0.1% to about 30% each, expressed as elemental metal based on the total weight of the composition, and more preferably about 0.1% to about 30% by weight each. 5 - about 15% by weight
It is. The above catalyst composition, which does not contain chromium oxide, has been found to be effective in converting C3 and/or C1 hydrocarbons to ethylene and propylene and selectively to ethylene. However, according to the present invention, the addition of chromium oxide not only extends the active life of the catalyst for the selective production of ethylene and ethane rather than propylene before catalyst regeneration is required. , ethylene, and ethane (which can be readily converted to ethylene) have been found to increase the selectivity to ethylene and ethane (which can be readily converted to ethylene). It has also been found that it is highly desirable to limit the amount of sulfur to 0.2% by weight. It is clear that the presence of such bound or fixed sulfur in the catalyst material tends to suppress the selectivity of the catalyst for the production of C2 hydrocarbons. Such sulfur is not clearly converted to hydrogen sulfide or otherwise lost during the hydrocarbon conversion process or regeneration step, and is probably present in the sulfate form, so it is not known to be "bound" or " It is called "fixed" sulfur.

The method of making the catalyst composition of the present invention appears to be unimportant as long as the desired final composition of the component metal oxides is obtained. Suitable manufacturing methods include slurry mixing, solution mixing, dry mixing, impregnation and coprecipitation, all of which are known to those skilled in the art. A preferred method is to add a metal solid such as base material MgO or Mg(OH)2 to a mixing device together with an aqueous solution of the active ingredient and/or promoter metal salt such as manganese nitrate, ferric nitrate, etc., and mix for several minutes. , for example 2
Mix for ~5 minutes to form a thick slurry.

For reasons of economy, excess water should be avoided. The resulting slurry is then heated to about 100°C to 15°C by conventional methods.
Air dry at 0°C, smoke at about 750'C to 800°C for about 4 hours, then mill, sieve and optionally pelletize or otherwise size by known means. It is also convenient to form the combination of the base and the other ingredients, usually the active ingredients, by slurrying and to impregnate the other ingredients with the mixture thus formed.

In accordance with another aspect of the invention, it has been found that steam is essential to carrying out the process when utilizing the above catalyst composition containing iron oxide. In particular, the presence of steam in converting C1 and C1 hydrocarbons greatly extends the active life of the catalyst, and the absence of steam for long periods of time reduces the iron oxide to metallic iron, which is not effective in the process. It was discovered that On the other hand, if the catalyst composition does not contain iron, it can be used without the presence of steam. However, it is preferred to use steam in these cases as well, as it has been found to extend the life of the catalyst before regeneration is required.

The process of the invention can be carried out in a fixed bed, moving bed, fluidized bed, suspended bubble column or spouted bed reactor. For experimental purposes, and in order to obtain clearly accurate measurements and precise control of process variables, the tests described in the examples below were carried out in a fixed bed reactor.

It has been found that during the implementation of the process of the invention a small amount of the feedstock becomes carbon, which is deposited on the catalyst and causes a reduction in the catalytic activity, in particular the ethylene selectivity. It is desirable to periodically regenerate the catalyst by conventional carbon removal techniques such as treatment with a containing gas; during such regeneration, an inert It may be desirable to use gas or steam dilution.

Following preparation of the catalyst composition, the catalyst may be prepared for use by purging with an inert gas such as nitrogen.
Typically, the catalyst is placed in a reactor, brought to reaction temperature by preheating with air, then purged with heated nitrogen, and finally introducing the feed hydrocarbon. It may be preferable to use steam rather than nitrogen as the purge gas since it is preferable to add steam to the purge gas. The catalyst may optionally be pretreated with hydrogen before use.

This treatment is preferably carried out at about the operating temperature of the process and at a pressure of up to about 600 psia. This hydrogen pretreatment appears to reduce the high oxidation states of manganese and/or iron, thus reducing initial carbon oxide formation.

The operating conditions of the process according to the invention appear to be less stringent, with the exception of operating temperature conditions. Accordingly, the following operating conditions have been found to be effective and are preferred.

If steam is used, the steam/hydrocarbon molar ratio may be from about 0.1/1 to about 1O/1, preferably about 0.5
/1 to about 5/1.

Hydrocarbon gas hourly space velocity (GH8V) is approximately 1ooh
-' to about 3000 h-', preferably from about 500 h to about 100 h.

The operating pressure may be from about 0.1 psia to about 100 psia, preferably from about 1 psia to about 60 psia.

Operating temperature appears to be significant in improving the conversion of feed hydrocarbons to olefins, especially ethylene selectivity. Suitable temperatures range from about 50°C to about 850°C, preferably from about 50°C to about 775°C.

The features and advantages of the invention are illustrated by the following example.

Quartz chips were used for a representative comparative test of pyrolysis in the presence of ``Fire-Crystal'' steam. Generally, all catalysts were prepared by the slurry method described above. For example, add Mg(OH)2 as a solid content to a mixing device and add the remaining components, e.g.
It was added as an aqueous solution of metal salts such as n(NO3)2 and Cr(Nov)s.9H,O. Although the active components and promoters were in oxide form, their concentrations are reported as weight percent of the metal element based on the total weight of the catalyst.

The reactor is 18mm+(i
, d,) was a fixed bed quartz reactor. The reactor had a quartz thermocouple insertion recess axially centered in the catalyst bed. The temperature reported is the temperature at the longitudinal center point of the catalyst bed.

In the experiments reported, all catalysts were pretreated in the same way.

The pretreatment was 10 minutes of air oxidation, 2 minutes of nitrogen purge, 10 minutes of hydrogen reduction, and a final nitrogen purge. The catalyst was allowed to rise to reaction temperature before introducing the feed hydrocarbons. The feed hydrocarbon was a lobe tun at a flow rate of 100 ee/min through a water saturator at about 81° C. resulting in a steam/feed hydrocarbon ratio of about 1/1. The combined feed hydrocarbon and steam flow rate passed through the catalyst bed with a residence time of approximately 1 second.

A small sample of the effluent stream from the reactor was taken and analyzed by chromatographic techniques. The reaction time after about 2 to 5 minutes is 6 conversions, which determines the initial activity of the catalyst, reported as mole % of n-butane converted. on a standardized mole basis of finished feedstock.

The test results for this yarn are reported in the table below.

0.5$Cr/3$Ca/4$Mn/Mg0711
3 76 41 15 25 4.40702
7 52 40 21 20 2.86710
20 55 35 29 16 1.767
11 35 55 33 32 15 1.5
0710 45 56 30 34 13 1
．． 26707 60 55 30 34 13
1.26710 80 58 28 36
12 1.113$Ca/4$Mn/880
718 3 69 42 17 23 3.
82729 7 62 36 29 13 1
．． 69728 20 63 33 33 11
1.33727 45 64 30 313
9 1.08728 85 66 29 3
7 9 1.03 quartz chip 720 2
-5 50 30 39 7 0.955$Cr/
f4g0 678 2-5 50
28 36 10 1.085gCr/Ca0
700 2-5 50 30 3
8 7 0.975XCr/La2(L+
698 2-5 50 20 28 8
1.00*C2 is ethane, C7- is ethylene and Cs
= represents propylene.

Typical is the pyrolysis test (quartz chips), in which the ratio of ethylene plus ethane to propylene is 1.00.
It should be observed that the vicinity of

Therefore, a higher ratio indicates selectivity to ethylene and ethane over propylene. As a result, Ca/Mn/MgO and Cr/C
Substantially higher ethylene plus ethane/propylene ratios were obtained for both a/Mn/MgO. - The best guideline is that when propylene production is equal to or exceeds ethylene production, especially when the ratio of ethylene plus ethane/propylene reaches 1.00 (thermal conversion using quartz chips), the catalyst are considered "active". On this basis, a catalyst containing chromium as a promoter will be active for about an hour before propylene production exceeds ethylene production, and even at 80 minutes of flow, without regeneration, this catalyst will , ethylene plus ethane/
It was found that the propylene ratio produced was substantially higher than thermal conversion using quartz chips. Furthermore, Ca/Mn
/MgO is an excellent catalyst for the process of the invention, but
It was observed that when it contained a small amount of chromium oxide as a promoter, it produced ethylene selectively over propylene for at least twice as long as a catalyst without chromium. The catalyst that did not contain this promoter began to reach thermal conversion after about 20 minutes.
The catalyst containing chromium oxide was still very effective at producing ethylene plus ethane but not propylene after 80 minutes.

The last three tests clearly show the ineffectiveness of the combination of chromium oxide and magnesium oxide, the combination of chromium oxide and calcium oxide, and the combination of chromium oxide and lanthanum oxide. It has also been found that magnesium oxide, lanthanum oxide, and cerium oxide alone provide essentially equivalent results to those obtained by thermal steam decomposition of n-butane in the presence of quartz chips.

``-m-・ Agent Patent Attorney Kyo Yuasa 3 ゛・-
11 (5 others)

Claims (34)

[Claims] (1) A catalyst composition suitable for converting a feed hydrocarbon comprising at least one of C_3 and C_4 hydrocarbons to a less saturated hydrocarbon, comprising: (a) at least one of (i) chromium; (ii) consisting essentially of at least one oxide of manganese and (iii) at least one oxide of magnesium; (b) (i) at least one oxide of chromium; (ii) at least one oxide of manganese; (iii) at least one lanthanum metal or at least one oxide of niobium; (c) (i) at least one oxide of chromium; (ii) at least one of at least one element of calcium, strontium, barium, tin, and antimony;
(iii) consisting essentially of at least one oxide of manganese and (iv) at least one oxide of magnesium; (d) (i) at least one oxide of chromium; (ii) at least one oxide of at least one element among calcium, strontium, barium, tin, and antimony; (iii) at least one oxide of manganese; and (iv) at least one (e) (i) at least one oxide of chromium; (ii) at least one oxide of iron; and (iii) at least one oxide of magnesium. (f) (i) at least one oxide of chromium; (ii) at least one oxide of iron; and (iii) at least one lanthanum-based metal; or at least one oxide of niobium; (g) (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) at least one oxide of manganese. (iv) at least one oxide of magnesium; or (h) (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) ) at least one oxide of manganese; and (iv) at least one lanthanum-based metal or at least one oxide of niobium. (2) The catalyst composition according to claim 1, wherein the catalyst composition comprises at least one lanthanum metal. (3) The catalyst composition according to claim 2, wherein the lanthanum-based metal is lanthanum or cerium. (4) At least one oxide of magnesium, lanthanum metal, or niobium is present in the composition in a major amount, and the remaining oxides are present in small amounts in claim 1.
Catalyst composition as described in . (5) The remaining oxides are each present in an amount of from about 0.1 to about 30% by weight, expressed as metal based on the total weight of the catalyst composition. Catalyst compositions as described. (6) Claims consisting essentially of (i) at least one oxide of chromium, (ii) at least one oxide of manganese, and (iii) at least one oxide of magnesium. Catalyst composition according to item 1. (7) A patent claim consisting of (i) at least one oxide of chromium, (ii) at least one oxide of manganese, and (iii) at least one lanthanum metal or at least one oxide of niobium. range 1
Catalyst composition as described in . (8) the catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of at least one element among calcium, strontium, barium, tin and antimony; and ( iii) Catalyst composition according to claim 1, consisting essentially of at least one oxide of magnesium. (9) the catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of at least one element among calcium, strontium, barium, tin and antimony; iii) Claim 1 consisting of at least one oxide of at least one lanthanum metal or niobium
Catalyst composition as described in . (10) the catalyst composition consists essentially of (i) at least one oxide of chromium; (ii) at least one oxide of iron; and (iii) at least one oxide of magnesium. A catalyst composition according to claim 1. (11) The catalyst composition comprises (i) at least one oxide of chromium, (ii) at least one oxide of iron, and (iii) at least one lanthanum metal or niobium. A catalyst composition according to scope 1. (12) the catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) at least one oxide of manganese; and (iv) at least one oxide of magnesium. A catalyst composition according to claim 1 consisting essentially of one oxide. (13) the catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) at least one oxide of manganese; and (iv) at least one oxide of manganese. A catalyst composition according to claim 1, comprising at least one oxide of a lanthanum metal or niobium. (14) A method for converting a feed hydrocarbon consisting of at least one of C_3 and C_4 hydrocarbons into a less saturated product hydrocarbon, comprising: (a) (i) chromium; consisting essentially of at least one oxide; (ii) at least one oxide of manganese; and (iii) at least one oxide of magnesium; (b) at least one of (i) chromium; (ii) at least one oxide of manganese; (iii) at least one oxide of lanthanum metal or niobium; (c) (i) at least one chromium; (ii) at least one oxide of at least one element among calcium, strontium, barium, tin and antimony; (iii) at least one oxide of manganese; and (iv) at least one of magnesium. consisting essentially of one oxide; (d) of (i) at least one oxide of chromium; (ii) of at least one of the elements calcium, strontium, barium, tin and antimony; (iii) at least one oxide of manganese, and (iv) at least one oxide of lanthanum metal or niobium; (e) (i) chromium; (ii) consisting essentially of at least one oxide of iron; and (iii) at least one oxide of magnesium; (f) at least one of (i) chromium; (ii) at least one oxide of iron; (iii) at least one lanthanum metal or at least one oxide of niobium; (g) (i) at least one chromium; (ii) at least one oxide of iron, (iii) at least one oxide of manganese, and (iv) at least one oxide of magnesium; or (h ) (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) at least one oxide of manganese; and (iv) at least one lanthanum metal or niobium. a catalyst composition comprising at least one oxide under conditions suitable for converting the feed hydrocarbon to a less saturated hydrocarbon, including the presence of steam for catalyst compositions (e)-(h); The above method, characterized in that the contacting is carried out at the bottom. (15) The method according to claim 14, wherein the catalyst composition comprises at least one lanthanum metal. (16) Claim 1, wherein the at least one lanthanum-based metal is at least one lanthanum and cerium.
The method described in Section 5. (17) the catalyst composition consists essentially of (i) at least one oxide of chromium; (ii) at least one oxide of manganese; and (iii) at least one oxide of magnesium. A method according to claim 14. (18) The catalyst composition comprises (i) at least one oxide of chromium, (ii) at least one oxide of manganese, and (iii) at least one oxidation of at least one lanthanum metal or niobium. Claim 1 consisting of a product
The method described in Section 4. (19) The catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one of at least one element of calcium, strontium, barium, tin, and antimony;
15. The method of claim 14, consisting essentially of an oxide of a species; (iii) at least one oxide of manganese; and (iv) at least one oxide of magnesium. (20) The catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of at least one element among calcium, strontium, barium, tin and antimony; (iii) ) at least one oxide of manganese; and (iv) at least one oxide of lanthanum metal or niobium.
The method described in section. (21) the catalyst composition consists essentially of (i) at least one oxide of chromium; (ii) at least one oxide of iron; and (iii) at least one oxide of magnesium. A method according to claim 14. (22) The catalyst composition comprises (i) at least one oxide of chromium, (ii) at least one oxide of iron, and (iii) at least one oxidation of at least one lanthanum metal or niobium. Claim 1 consisting of a product
The method described in Section 4. (23) the catalyst composition comprises: (i) at least one oxide of chromium; (ii) at least one oxide of iron; (iii) at least one oxide of manganese; and (iv) at least one oxide of magnesium. 15. The method of claim 14, consisting essentially of one oxide. (24) The catalyst composition comprises (i) at least one oxide of chromium, (ii) at least one oxide of iron, (iii) at least one oxide of manganese, and (iv) at least one oxide of manganese. Claim 14 consisting of at least one oxide of lanthanum metal or niobium
The method described in section. (25) At least one oxide among magnesium, lanthanum metals, or niobium is present in the composition in a major amount, and the remaining oxides are present in small amounts in claim 1.
The method according to any one of Items 4 to 24. (26) The remaining oxide is about 0.1 to about 30% by weight, expressed as metal based on the total weight of the catalyst composition.
26. The method of claim 25, wherein each is present in an amount of . (27) The method according to any one of claims 14 to 26, wherein the temperature is maintained at about 550 to about 850°C. (28) The process was carried out at a steam/feed hydrocarbon ratio of about 0.
28. A method according to any of claims 14 to 27, carried out in the presence of 1/1 to about 10/1 steam. (29) The sulfur content of the catalyst compositions (a) and (b) is expressed in terms of elemental sulfur based on the total weight of the catalyst,
29. The method of any of claims 14-28, wherein the amount is about 0.2% by weight or less. (30) The method according to any one of claims 14 to 29, wherein the hydrocarbon supplied is propane. (31) The method according to any one of claims 14 to 29, wherein the hydrocarbon supplied is butane. (32) The method according to any one of claims 14 to 29, wherein the hydrocarbon feed comprises a mixture of propane and butane. (33) The conditions are suitable for selectively converting the feed hydrocarbons to ethylene and ethane.
The method according to any one of Items 4 to 32. 34. The method of claim 33, wherein the conditions are suitable to selectively convert the feed hydrocarbon to ethylene.